Pyridyloxy-phenoxyalkanecarboxylic acid derivatives and their herbicidal use

ABSTRACT

Herbicidal and plant growth-regulating pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula ##STR1## wherein A is cyano or carboxyl, an ester, thioester or amido radical or the salt of the carboxylic acid with a cation or a quaternary ammonium group, 
     Z is hydrogen, halogen, cyano, nitro, C 1  -C 4  alkyl or C 1  -C 4  alkoxy, 
     D is hydrogen, halogen, cyano, nitro or C 1  -C 4  alkoxy, 
     E is halogen, trifluoromethyl or cyano. 
     R 1  is hydrogen, C 1  -C 4  alkyl, C 2  -C 8  alkoxyalkyl or C 1  -C 5  alkoxy carbonyl and 
     R 2  is hydrogen or C 1  -C 4  alkyl.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 140,402 filed on Apr. 14, 1980 U.S. Pat. No. 4,329,167 issued Nov. 11, 1982, which is a continuation-in-part of application Ser. No. 080,965, filed on Oct. 1, 1979, now abandoned. Application Ser. No. 080,965 was a continuation of application Ser. No. 919,119, filed on June 26, 1978, now abandoned.

The present invention relates to novel pyridyloxy-phenoxyalkanecarboxylic acid derivatives which have a herbicidal and plant growth-regulating action, processes for their production, compositions which contain these compounds as active ingredients, and to a method of selectively controlling weeds and of regulating plant growth which comprises the use of the novel active substances or of compositions which contain them.

The active compounds of the present invention have the formula I ##STR2## wherein A represents the cyano group, a radical --COB or a 2-oxazoline radical which is unsubstituted or mono- or polysubstituted by methyl,

B represents radical --OR₃, --SR₃, --NR₄ R₅ or --O--N═C (C₁ -C₄ alkyl)₂

Z and D each individually represent hydrogen, halogen, cyano, nitro, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

E represents halogen, trifluoromethyl, cyano or nitro,

R₁ represents hydrogen, C₁ -C₄ alkyl or C₂ -C₁₈ alkoxyalkyl, or C₁ -C₅ alkoxycarbonyl

R₂ represents hydrogen or C₁ -C₄ alkyl,

R₃ represents hydrogen, ammonium or an alkali or alkaline earth metal cation, a benzyl or C₁ -C₄ alkylammonio group, whose alkyl radicals may be substituted by hydroxyl C₁ -C₄ alkoxy or

a C₁ -C₁₈ alkyl radical which is unsubstituted or substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxyalkoxy, C₂ -C₈ alkoxycarbonyl, bis(C₁ -C₄ alkyl)amino, C₃ -C₈ cycloalkyl, C₃ -C₈ cycloalkenyl and also by a 5 to 6-membered heterocyclic radical which is unsubstituted or is itself mono- or polysubstituted by C₁ -C₄ alkyl;

a C₃ -C₁₀ alkenyl radical which is unsubstituted or mono- to tetrasubstituted by halogen;

a C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl- or C₃ -C₈ cycloalkenyl radical;

a phenyl or benzyl radical, which is mono- or polysubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, nitro, trifluoromethyl, cyano, carboxyl, sulfonyl, hydroxyl, amino or bis(C₁ -C₄ alkyl)amino;

a 5 to 6-membered heterocyclic radical;

R₄ represents hydrogen, a C₁ -C₈ alkyl radical, unsubstituted or substituted by halogen, hydroxyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄ alkoxycarbonyl;

C₃ -C₈ alkenyl, unsubstituted or halogensubstituted;

C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl or C₃ -C₈ cycloalkenyl;

phenyl or benzyl, unsubstituted or substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethyl, nitro or cyano;

R₅ represents the same as R₄ or C₁ -C₄ alkoxy or C₂ -C₄ alkenyloxy or

R₄ and R₅ together with the nitrogen atom, to which they are attached, form also a 5 to 6-membered heterocyclic ring, which may be substituted by C₁ -C₄ alkyl.

In the above formula the alkyl radicals can be branched or unbranched and contain the indicated number of carbon atoms. The heterocyclic radicals R₃ include, furyl-, tetrahydrofuryl-, oxane-, thiophene-radicals and further, the same that are also found by the symbols R₄ and R₅ with the nitrogen to which they are attached, pyrrolidine, pyridine, piperidine, morpholine, oxazoline or piperazine. These rings may be substituted by C₁ -C₄ alkyl radicals.

The active compounds of the formula (I) of the present invention possess a herbical action, especially in post-emergent application, and can be used as weed-killers in crops of mono- and dicotyledonous plants. They also possess advantageous growth-regulating effects (growth inhibition). In particular, they inhibit the growth of dicotyledonous plants. Exemplary of the useful application of the compounds of the present invention are:

the reduction of the vegetative growth in soya and similar leguminosae, resulting in an increase in the yield of these plants;

the inhibition of the undesirable growth of suckers in tobacco plants, the leading shoots of which have been cut, thus promoting the formation of larger and finer leaves;

the inhibition of the growth of grass and dicotyledonous plants, such as fruit trees, ornamental trees, bushes and hedgerows, with the object of saving cutting work.

The compounds of the present invention have a low toxicity to warm-blooded animals and their application causes no problems. The rate of application is between 0.1 and 5 kg per hectare.

Good herbicidal activity has been observed with the groups of compounds listed below. They are therefore of special interest among the compounds of formula I. ##STR3##

In these formulae, B has the meanings given above under formula I.

From the U.S. Pat. Nos. 4,046,553 and 4,105,435 have become know 4-pyridyloxy-phenoxyalkanecarboxylic acid derivatives with herbicidal activity. The compounds of this invention proved to act differently and are capable of controlling plants, which were not or not satisfactorily controlled with compounds known from these patents.

The novel compounds of the formula (I) can be obtained by processes which are in themselves known. In a first process, a substituted or unsubstituted halopyridine of the formula II, ##STR4## wherein D and E are as defined in formula (I) and Hal represents a halogen atom, preferably a chlorine or bromine atom, is reacted with a hydroxyphenoxyalkanecarboxylic acid derivative of the formula III, ##STR5## wherein A, Z, R₁ and R₂ are as defined in formula (I), in the presence of an acid acceptor.

Such reactions are in themselves known and the exact method by which they are carried out is described in the literature, for example in Houben-Weyl, Volume 3, page 85 ff.

In a second process, the pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula (I) are prepared by reacting a pyridyloxy-hydroxyphenyl ether of the formula IV, ##STR6## wherein Z, D and E are as defined in formula (I), with an α-halogenocarboxylic acid derivative of the formula V ##STR7## wherein A, R₁ and R₂ are as defined in formula (I) and Hal represents a halogen atom, preferably a chlorine or bromine atom, in the presence of an acid acceptor.

The above reactions can be carried out in the presence or absence of solvents or diluents which are intert to the reactants. Polar organic solvents, such as methyl ethyl ketone, acetonitrile, dimethyl formamide, dimethyl sulphoxide etc., are preferred. The reaction temperatures are between 0° and 200° C. and the reaction time is from 1/4 hour to several days, depending on the chosen reaction temperature and solvent. The reaction is ordinarily carried out under normal pressure or slight excess pressure. Suitable acid acceptors for the reaction are inorganic bases, for example NaOH, KOH, NaOCH₃, NaH, K₂ CO₃, potassium tert-butylate etc., and also organic bases.

A number of the starting materials of the formulae (II) to (V) are known. Starting materials of these formulae which have not yet been described can be easily prepared by conventional processes and techniques.

Substituted 2-halogeno-pyridines of the formula (II) can be easily obtained from the corresponding 2-pyridinoles, some of which are known. Starting materials of the formula (III) can be obtained by reacting, for example, a monobenzyl ether of an optionally substituted resorcinol with an α-halogenocarboxylic acid derivative, preferably an ester of the formula (V), and cleaving the benzyl-phenyl ether bond by catalytic hydrogenation, for example with a palladium on carbon catalyst, whereby the benzyl radical is removed as toluene.

The starting materials of the formula (IV) can be obtained by reaction of resorcinol with halopyridines in equimolar amounts and in the presence of a base.

Carboxylic acid derivatives of the formula (V) are also known. As their simplest representatives, mention may be made for example of chloroacetic acid and the esters, thioesters and amides theroef. However, other α-halocarboxylic acid derivatives substituted in accordance with R₁ and R₂ are also suitable.

The following Examples illustrate the process of the present invention for obtaining arbitrarily chosen active compounds of the formula (I). Further active compounds which are obtained in corresponding manner are listed in the subsequent tables.

These pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula (I) are stable compounds which are soluble in conventional organic solvents, such as alcohols, ethers, ketones, dimethyl formamide, dimethyl sulphoxide etc.

EXAMPLE 1 α-[3-(3',5'-Dichloropyrid-2-yl)-oxy-phenoxy] propionic acid methyl ester (intermediate) ##STR8##

30.8 g (0.1 mole) of 3-(3',5'-dichloropyrid-2'-yl)-oxy-phenoxy phenol, 18.2 g (0.13 mole) of potassium carbonate and 22 g of methyl α-bromopropionate are refluxed in 300 ml of ethyl ketone for 3 hours. The inorganic salts are then filtered off and the filtrate is concentrated. Recrystallisation of the residue from ether/petroleum ether affords 29 g (70% of theory) of the title product with a melting point of 58°-60° C.

EXAMPLE 2 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid methyl ester ##STR9##

(a) 171 g (0.5 mole) of α-[3-(3',5'-dichloropyrid-2-yl)oxy-phenoxy] propionic acid (prepared according to Example 1) are dissolved in 250 ml of 1,2 dichloroethane. The reaction is then cooled to -12° to -14° C. and during 2 hours there is added dropwise 250 ml of 100% nitric acid. After 1/2 hour, the reaction mixture is poured into ice-water. The mixture is then extracted methylene chloride. The organic phase is washed twice with water, dried over magnesium sulfate and evaporated. The residue is taken up in 500 ml of hexane and triturated, which causes it to crystallise. The cristals are filtered and dried to yield 172.3 g (89% of theory) of the title compound which melts at 107°-108° C.

This compound can also be produced in the following manner.

(b) 30.1 g (0.1 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenol, 16.7 g (0.1 mole) of methyl α-bromopropionate and 20.7 g (0.15 mole) of potassium carbonate are refluxed for 14 hours in 400 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual brown oil is taken up in chloroform and filtered over a short column of silica gel, affording 22.4 g (58% of theory) of title product which melts at 107° C. after recrystallisation from hexane.

EXAMPLE 3 3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenyl acetate (intermediate)

A mixture of 256 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.9 liters of glacial acetic acid and 280 ml of acetic anhydride is stirred for 12 hours at reflux temperature. The solution is cooled to 40° C., then 81 g of sodium acetate are added with stirring and 106 g of chlorine gas are introduced at 40° C. in the course of 7 hours. Excess chlorine gas is removed by introducing nitrogen for 2 hours and the solution is concentrated. The ethyl acetate solution (1000 ml) of the oily residue is washed with water and saturated NaHCO₃ solution and concentrated, affording 343 g of the title compound as a brown oil which crystallises spontaneously on trituration with petroleum ether. Melting point: 71°-75° C.

EXAMPLE 4 3-(3',5'-Dichloropyridyl-2'-oxy)-6- and 4-chlorophenol (intermediate)

A suspension of 2.26 g of powdered KOH and 10 g of 3-(3',5'-dichloropyridyl-2'-oxy)-6-phenyl acetate in 30 ml of absolute methanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere, cooled to room temperature, acidified with 3.7 ml of concentrated hydrochloric acid and concentrated. The toluene solution (50 ml) of the residue is washed with water, dried, filtered over activated carbon and concentrated, affording 8.4 g of an oil which consists of a mixture of the 6-chlorophenol and 4-chlorophenol isomers in the ratio 7:3.

EXAMPLE 5 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid methyl ester ##STR10##

25 g (0.085 mole) of a mixture of 3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenol and 3-(3',5'-dichloropyridyl-2'-oxy)-4-chlorophenol (prepared according to Example 4), 14.2 g (0.085 mole) of methyl α-bromopropionate and 13.8 g (0.1 mole) of potassium carbonate are refluxed for 6 hours in 250 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual yellow oil is recrystallised from ether/petroleum ether, affording 30.1 g (94% of theory) if isomer-free title product with a melting point of 82°-83° C.

EXAMPLE 6 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenyl acetate (intermediate)

A mixture of 205 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.1 liters of glacial acetic acid and 224 ml of acetic anhydride is stirred for 12 hours at reflux temperature. The solution is cooled to 60° C., then 64.8 g of sodium acetate are added with stirring and a solution of 102 ml of bromine in 400 ml of glacial acetic acid are added dropwise at 60° C. in the course of 53/4 hours. The solution is concentrated and the residue is dissolved in ethyl acetate. The organic phase is washed in succession with water and saturated NaHCO₃ solution. The combined ethyl acetate extracts are dried and concentrated, affording 302.5 g of an oil which crystallises on being covered with a layer of petroleum ether (b.p. 60°-90° C.). After recrystallisation from cyclohexane, the title product melts at 106°-107° C.

EXAMPLE 7 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenol (intermediate)

A suspension of 28 g of powdered KOH and 153.5 g of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenyl acetate in one liter of absolute methanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere and concentrated. The concentrate is acidified at room temperature with concentrated hydrochloric acid and evaporated to dryness. The toluene solution (400 ml) of the residue is washed with water, dried, and concentrated. The oily residue is triturated with petroleum ether/cyclohexane and filtered, affording 137 g of the crystalline title product with a melting point of 93°-95° C.

EXAMPLE 8 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy] propionic acid methyl ester ##STR11##

50.2 g (0.15 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenol (prepared according to Example 7), 27.5 g (0.165 mole) of methyl α-bromopropionated and 27.6 g (0.2 mole) of potassium carbonate are refluxed for 5 hours in 250 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual reddish oil is recrystallised from ether/petroleum ether, affording 58 g (91.8% of theory) of the title compound with a melting point of 75° C.

Analogously to these Examples, the following compound can be prepared:

    ______________________________________                                         No.     B                    phys. data                                        ______________________________________                                          ##STR12##                                                                     1       OCH.sub.3            m.p. 82-83°                                2       OC.sub.2 H.sub.5     m.p. 53-56°                                3       OC.sub.3 H.sub.7 iso n.sub.D.sup.25 1.5567                             4       OC.sub.3 H.sub.7 n                                                     5       OC.sub.4 H.sub.9 n   n.sub.D.sup.25 1.5540                             6       OC.sub.4 H.sub.9 sec.                                                                               n.sub.D.sup.25 1.5525                             7       OC.sub.4 H.sub.9 tert.                                                 8       OC.sub.4 H.sub.9 iso n.sub.D.sup.25 1.5538                             9       OCH(CH.sub.3)C.sub.3 H.sub.7 n                                         10      OCH(CH.sub.3)C.sub.5 H.sub.11 n                                        11      OC.sub.8 H.sub.17 n                                                    12      OC.sub.2 H.sub.4 OCH.sub.3                                                                          n.sub.D.sup.25 1.5547                             13      OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      14      OC.sub.2 H.sub.4 Cl  n.sub.D.sup.25 1.5722                             15      OC.sub.2 H.sub.4 Br                                                    16                                                                                      ##STR13##           n.sub.D.sup.30 1.5617                             17                                                                                      ##STR14##                                                             18                                                                                      ##STR15##           n.sub.D.sup.30 1.5565                             19      OCH.sub.2 CHCH.sub.2 n.sub.D.sup.25 1.5629                             20      OC.sub.2 H.sub.4CHCH.sub.2                                             21      OCH.sub.2 C(CH.sub.3)CH.sub.2                                          22      OCH.sub.2 CCH        m.p. 64-68°                                23      OCH(CH.sub.3)CCH                                                       24                                                                                      ##STR16##                                                             25                                                                                      ##STR17##                                                             26      OCH.sub.2 CN                                                           27      OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                                                 n.sub.D.sup.30 1.5445                             28      SCH.sub.3            n.sub.D.sup.25 1.5850                             29      SC.sub.2 H.sub.5                                                       30      SC.sub. 3 H.sub.7 n                                                    31      SC.sub.3 H.sub.7 iso                                                   32      SC.sub.4 H.sub.9 iso                                                   33      SCH.sub.2 CHCH.sub.2                                                   34      SCH.sub.2CHCHCH.sub.3                                                  35      SCH.sub.2 COOCH.sub.3                                                                               n.sub.D.sup.40 1.5788                             36                                                                                      ##STR18##                                                             37      O.sup.⊖ Na.sup.⊕                                                                        m.p. 98-101°                               38      O.sup.⊖ NH.sub.4.sup.⊕                                     39      NH.sub.2             m.p. 142-5°                                40      N(CH.sub.3).sub.2                                                      41      NHC.sub.2 H.sub.5    m.p. 112-5°                                42      NHC.sub.2 H.sub.4 OH                                                   43      NH(CH.sub.2).sub.3 OCH.sub.3                                                                        m.p. 90-92°                                44      NHC.sub.2 H.sub.4 OCH.sub.3                                                                         m.p. 89-91°                                45      NHC.sub.2 H.sub.4 Cl                                                   46      NHCH.sub.2 CHCH.sub.2                                                                               m.p. 119-120°                              47      N(CH.sub.2 CHCH.sub.2).sub.2                                           48      NHC.sub.3 H.sub.7 iso                                                  49      N(C.sub.2 H.sub.5).sub.2                                                                            m.p. 73-4°                                 50      NHC.sub.4 H.sub.9 n                                                    51      NHC.sub.5 H.sub.11 iso                                                 52                                                                                      ##STR19##                                                             53                                                                                      ##STR20##           m.p. 39-42°                                54      NHCH.sub.2 COOC.sub.2 H.sub.5                                          55      N(CH.sub.3)OCH.sub.3 m.p. 75-7°                                 56      ONC(CH.sub.3)C.sub.2 H.sub.5                                           57      ONC(CH.sub.3).sub.2                                                    58                                                                                      ##STR21##                                                              ##STR22##                                                                     59      OCH.sub.3                                                              60      OC.sub.2 H.sub.5                                                       61      OCH.sub.2CHCH.sub.2                                                    62      OC.sub.3 H.sub.6 OCH.sub.3                                             63      SCH.sub.3                                                              64      SCH.sub.2 CCH                                                          65      NHCH.sub.3                                                             66      N(CH.sub.3)OCH.sub.3 n.sub.D.sup.30 1.5613                              ##STR23##                                                                     67      OCH.sub.3            m.p. 88-89°                                68      OC.sub.2 H.sub.5     n.sub.D.sup.30 1.5620                             69      OC.sub.3 H.sub.7 iso n.sub.D.sup.30 1.5563                             70      OC.sub.4 H.sub.9 iso                                                   71      OC.sub.2 H.sub.4 OCH.sub.3                                             72      OCH.sub.2 CN                                                           73      ONC(CH.sub.3).sub.2                                                    74      OCH.sub.2 COOCH.sub.3                                                  75      SCH.sub.3                                                              76      SC.sub.3 H.sub.7 iso                                                   77      SC.sub.5 H.sub.11 n                                                    78      NH.sub.2                                                               79      NHC.sub.2 H.sub.5    m.p. 104-5°                                80      N(C.sub.2 H.sub.5).sub.2                                               81      NHCH.sub.3                                                             82      NHCH.sub.2 CHCH.sub.2                                                  83      NHCH.sub.2 CCH                                                         84      N(CH.sub.3)OCH.sub.3 n.sub.D.sup.25 1.5660                             85                                                                                      ##STR24##                                                             86                                                                                      ##STR25##                                                              ##STR26##                                                                     87      OCH.sub.3            m.p. 107-8°                                88      OC.sub.2 H.sub.5                                                       89      OC.sub.3 H.sub.7 n                                                     90      OC.sub.3 H.sub.7 iso n.sub.D.sup.30 1.5638                             91      OC.sub.4 H.sub.9 n                                                     92      OC.sub.4 H.sub.9 sec.                                                                               n.sub.D.sup.30 1.5630                             93      OCH(CH.sub.3)C.sub.4 H.sub.9 n                                         94      OC.sub.8 H.sub.17 n                                                    95      OC.sub.2 H.sub.4 OCH.sub.3                                                                          n.sub.D.sup.30 1.5709                             96      OCH(CH.sub.3)COOCH.sub.3                                               97      OC.sub.2 H.sub.4 Cl                                                    98      OCH.sub.2 CHCH.sub.2 n.sub.D.sup.30 1.5771                             99      OCH.sub.2 C(CH.sub.3)CH.sub.2                                          100     OCH.sub.2 CCH                                                          101                                                                                     ##STR27##                                                             102     OCH(CH.sub.3)CCH                                                       103     OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                  n.sub.D.sup.40 1.5699                             104                                                                                     ##STR28##                                                             105                                                                                     ##STR29##                                                             106     SCH.sub.3                                                              107     SC.sub.2 H.sub.5                                                       108     SC.sub.4 H.sub.9 iso                                                   109     SCH.sub.2 CHCH.sub.2                                                   110     SCH.sub.2 C(CH.sub.3)CH.sub.2                                                                       n.sub.D.sup.30 1.5920                             111     SCH.sub.2 CCH        m.p. 92-95°                                112     NH.sub.2             m.p. 135-7°                                113     NHCH.sub.3           m.p. 126-7°                                114     N(CH.sub.3).sub.2    m.p. 116-7°                                115     NHC.sub.2 H.sub.5    m.p. 128-9°                                116     N(C.sub.2 H.sub.5).sub.2                                                                            m.p. 88-9°                                 117     NHC.sub.3 H.sub. 7 n m.p. 112-4°                                118     NHC.sub.3 H.sub.7 iso                                                                               m.p. 112-3°                                119     NHCH.sub.2 CHCH.sub.2                                                                               m.p. 108-11°                               120     N(CH.sub.2 CHCH.sub.2).sub.2                                                                        n.sub.D.sup.30 1.5760                             121     NHCH.sub.2 CCH       m.p. 148-150°                              122     NHC.sub.4 H.sub.9 n                                                    123     NHC.sub.4 H.sub.9 sec.                                                 124     NHC.sub.4 H.sub.9 iso                                                  125     NHC.sub.5 H.sub.11 iso                                                                              m.p. 95-98°                                126     NHC.sub.6 H.sub.13 n m.p. 87-90°                                127     NHC.sub.2 H.sub.4 OCH.sub.3                                                                         m.p. 101-3°                                128     NH(CH.sub.3)OCH.sub.3                                                                               m.p. 93-4°                                 129     NHC(CH.sub.3).sub.2 CCH                                                                             m.p. 118-120°                              130     NHCH.sub.2 COOC.sub.2 H.sub.5                                          131                                                                                     ##STR30##           m.p. 116-8°                                132                                                                                     ##STR31##           m.p. 118-120°                              133                                                                                     ##STR32##           m.p. 113-116°                              134                                                                                     ##STR33##           m.p. 132-134°                              135                                                                                     ##STR34##           m.p. 130-132°                              136                                                                                     ##STR35##                                                             137                                                                                     ##STR36##           m.p. 148-151°                              138                                                                                     ##STR37##           m.p. 134-137°                              139                                                                                     ##STR38##           m.p. 117-119°                              140     NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     141     NHC.sub.3 H.sub.6 OCH.sub.3                                                                         n.sub.D.sup.40 1.5738                             142     NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     143     NHC.sub.8 H.sub.17 n                                                   144     OH                   m.p. 134-6°                                145     O.sup.⊖ NH.sub.3 C.sub.3 H.sub.7 iso                           146     ONC(CH.sub.3).sub.2                                                     ##STR39##                                                                     147     OH                                                                     148     OCH.sub.3            m.p. 80-2°                                 149     OC.sub.2 H.sub.5     n.sub.D.sup.25 1.5511                             150     OC.sub.3 H.sub.7 n                                                     151     OC.sub.3 H.sub.7 iso n.sub.D.sup.30 1.5585                             152     OC.sub.4 H.sub.9 n                                                     153     OC.sub.4 H.sub.9 sec.                                                                               n.sub.D.sup.30 1.5590                             154     OC.sub.2 H.sub.4 Cl                                                    155     OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                  n.sub.D.sup.30 1.5715                             156                                                                                     ##STR40##                                                             157     OC.sub.2 H.sub.4 OCH.sub.3                                             158     OC.sub.3 H.sub.6 OCH.sub.3                                             159     OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                    160     OCH.sub.2 CN                                                           161     OCH(CH.sub.3)COOC.sub.2 H.sub.5                                                                     n.sub.D.sup.30 1.5525                             162     ONC(CH.sub.3).sub.2  n.sub.D.sup.30 1.5665                             163     OCH.sub.2 CHCH.sub.2 n.sub.D.sup.30 1.5735                             164     OCH.sub.2 CHCHCH.sub.3                                                 165     OCH(CH.sub.3)CHCH.sub.2                                                166     OCH.sub.2 CCH        n.sub.D.sup.30 1.5795                             167     OC(CH.sub.3).sub.2 CCH                                                 168                                                                                     ##STR41##                                                             169                                                                                     ##STR42##                                                             170                                                                                     ##STR43##           m.p. 145-7°                                171                                                                                     ##STR44##                                                             172     SCH.sub.3            n.sub.D.sup.30 1.6015                             173     SC.sub.2 H.sub.5     n.sub.D.sup.30 1.5933                             174     SC.sub.4 H.sub.9 iso                                                   175     SCH.sub.2 COOCH.sub.3                                                  176     NH.sub.2             m.p. 156-9°                                177     NHCH.sub.3           m.p. 132-4°                                178     N(CH.sub.3).sub.2    m.p. 118-120°                              179     NHC.sub.2 H.sub.5                                                      180     N(C.sub.2 H.sub.5).sub.2                                               181     NHC.sub.3 H.sub.7 iso                                                  182                                                                                     ##STR45##                                                             183     NHCH.sub.2 COOCH.sub.3                                                 184                                                                                     ##STR46##                                                             185                                                                                     ##STR47##                                                             186     NHC.sub.2 H.sub.4 OCH.sub.3                                                                         m.p. 118-120°                              187     NHC.sub.3 H.sub.6 OCH.sub.3                                                                         m.p. 90-92°                                188     NHCH.sub.2 CHCH.sub.2                                                                               m.p. 104-6°                                189     N(CH.sub.2 CHCH.sub.2).sub.2                                           190     N(CH.sub.3)OCH.sub.3 n.sub.D.sup.30 1.5800                             191     NHOCH.sub.2 CHCH.sub.2                                                  ##STR48##                                                                     192     OCH.sub.3            m.p. 75°                                   193     OC.sub.2 H.sub.5                                                       194     OC.sub.3 H.sub.7 iso m.p. 60-3°                                 195     OCH(CH.sub.3)C.sub.3 H.sub.7 n                                                                      n.sub.D.sup.30 1.5561                             196     OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                                   n.sub.D.sup.30 1.5631                             197     OC.sub.2 H.sub.4 Cl  n.sub.D.sup.30 1.5792                             198     OC.sub.8 H.sub.17 n  n.sub.D.sup.30 1.5458                             199     OCH.sub.2 CHCHCH.sub.3                                                                              n.sub.D.sup.30 1.5730                             200     OCH.sub.2 CCH        m.p. 80-82°                                201                                                                                     ##STR49##           n.sub.D.sup.30 1.5811                             202     SC.sub.3 H.sub.7 iso n.sub.D.sup.30 1.5795                             203     SC.sub.4 H.sub.9 iso n.sub.D.sup.30 1.5805                             204     SCH.sub.2 COOCH.sub.3                                                                               n.sub.D.sup.30 1.5780                             205     SCH(CH.sub.3)C.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5778                             206     NH.sub.2             m.p. 155-156°                              207     NHC.sub.2 H.sub.5    m.p. 114-115°                              208     N(CH.sub.3)OCH.sub.3                                                   209     OH                   m.p. 150-1°                                 ##STR50##                                                                     210     OCH.sub.3            m.p. 74-77°                                211     OC.sub.2 H.sub.5                                                       212     OC.sub.3 H.sub.7 n                                                     213     OC.sub.3 H.sub.7 iso                                                   214     OC.sub.4 H.sub.9 iso                                                   215     OC.sub.6 H.sub.13 n                                                    216     OC.sub.2 H.sub.4 Cl                                                    217     OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                     218     OC.sub.2 H.sub.4 OC.sub.4 H.sub.9                                      219                                                                                     ##STR51##                                                             220                                                                                     ##STR52##                                                             221                                                                                     ##STR53##                                                             222     OCH.sub.2 CHCH.sub.2                                                   223     OCH(CH.sub.3)CHCH.sub.2                                                224     OCH.sub.2 CCH                                                          225     OCH(CH.sub.3)CCH                                                       226     SCH.sub.3                                                              227     SCH.sub.2 CHCH.sub.2                                                   228     SCH(CH.sub.3)CHCH.sub.2                                                229     SCH.sub.2 CCH                                                          230                                                                                     ##STR54##                                                             231                                                                                     ##STR55##                                                             232     OH                                                                     233     O.sup.⊖ H.sub.3 N.sup.⊕ (C.sub.3 H.sub.7 iso).sub.2        234     O.sup.⊖ Na.sup.⊕                                           235     O.sup.⊖ NH.sub.4.sup.⊕                                     236     NH.sub.2                                                               237     NHCH.sub.3                                                             238     N(C.sub.2 H.sub.5).sub.2                                               239     NHC.sub.4 H.sub.9 iso                                                  240     NHC.sub.2 H.sub.4 OCH.sub.3                                            241     NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     242     N(CH.sub.3)OCH.sub.3                                                    ##STR56##                                                                     243     OH                                                                     244     OCH.sub.3                                                              245     OC.sub.3 H.sub.7 iso                                                   246     OC.sub.4 H.sub.9 n                                                     247     SCH.sub.3                                                              248     SCH.sub.2CHCH.sub.2                                                    249     SCH.sub.2 COOCH.sub.3                                                  250     SC.sub.2 H.sub.4 OCH.sub.3                                             251     SC.sub.4 H.sub.9 iso                                                   252                                                                                     ##STR57##                                                             253                                                                                     ##STR58##                                                             254     NH.sub.2                                                               255     NHC.sub.2 H.sub.5                                                      256     N(CH.sub.3).sub.2                                                      257     NHCH.sub.2 CHCH.sub. 2                                                 258     N(CH.sub.3)OCH.sub.3                                                   259     NHC.sub.5 H.sub.11 n                                                    ##STR59##                                                                     260     OH                                                                     261     OCH.sub.3            n.sub.D.sup.25 1.5150                             262     OC.sub.2 H.sub.5                                                       263     OC.sub.3 H.sub.7 n                                                     264     OC.sub.3 H.sub.7 iso                                                   265     OCH.sub.2 CHCH.sub.2                                                   266     OCH.sub.2 CCH                                                          267     OCH(CH.sub.3)COOC.sub.2 H.sub.5                                        268     NH.sub.2                                                               269     NHCH.sub.3                                                             270     N(CH.sub.3).sub.2                                                      271     N(C.sub.3 H.sub.7 iso).sub.2                                           272     NHCH.sub.2 CHCH.sub.2                                                  273     NHCH.sub.2 CHCH                                                         ##STR60##                                                                     274     OH                                                                     275     OCH.sub.3            m.p. 74-75°                                276     OC.sub.2 H.sub.5                                                       277     OCH.sub.2 CN                                                           278     OC.sub.3 H.sub.7 n                                                     279     OC.sub.3 H.sub.7 iso                                                   280     OC.sub.4 H.sub.9 n                                                     281     OCH.sub.2 CHCH.sub.2                                                   282     OCH.sub.2 CHCHCH.sub.3                                                 283     OCH.sub.2 CCH                                                          284     SCH.sub.3                                                              285     SC.sub.2 H.sub.5                                                       286     SC.sub.3 H.sub.7 iso                                                   287     SCH.sub.2 CN                                                           288     SCH.sub.2 COOCH.sub.3                                                  289     NH.sub.2                                                               290     NHCH.sub.3                                                             291     N(CH.sub.3).sub.2                                                      292     NH(C.sub.3 H.sub.7 iso)                                                293     NHCH.sub.2 CHCH.sub.2                                                  294                                                                                     ##STR61##                                                              ##STR62##                                                                     295     OH                                                                     296     OCH.sub.3                                                              297     OC.sub.2 H.sub.5     n.sub.D.sup.30 1.5223                             298     OC.sub.3 H.sub.7 n                                                     299     OC.sub.4 H.sub.9 iso                                                   300     OCH.sub.2 CHCH.sub.2                                                   301     OCH.sub.2 CCH                                                          302     OCH(CH.sub.3)CCH                                                       303     OC.sub.4 H.sub.9 n                                                     304     OC.sub.4 H.sub.9 tert.                                                 305     OC.sub.4 H.sub.9 sec.                                                  306     OC.sub.2 H.sub.4 OCH.sub.3                                             307     OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                    308     OC.sub.2 H.sub.4 Cl                                                    309     OC.sub.2 H.sub.4 Br                                                    310     OCH.sub.2 CHCHCH.sub.2 Cl                                              311     OCH.sub.2 C(CH.sub.3)CH.sub.2                                          312     OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                     313     OC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                              314     OCH(CH.sub.3)COOC.sub.2 H.sub.5                                        315     OCH(C.sub.2 H.sub.5).sub.2                                             316     SH                                                                     317     SCH.sub.3                                                              318     SC.sub.2 H.sub.5                                                       319     SCH.sub.2 COOC.sub.2 H.sub.5                                           320     SCH.sub.2 CHCH.sub.2                                                   321     SCH.sub.2 CCH                                                          322     SC.sub.4 H.sub.9 n                                                     323     SCH.sub.2CH(CH.sub.3)CH.sub.2                                          324     SCH(CH.sub.3)C CH                                                      325     NH.sub.2             m.p. 127-128°                              326     NHC.sub.2 H.sub.4 OCH.sub.3                                            327     NHC.sub.3 H.sub.6 OCH.sub.3                                            328     N(C.sub.2 H.sub.4 OH).sub.2                                            329     NHC.sub.2 H.sub.4 COOCH.sub.3                                          330     NHCH.sub.2 COOCH.sub.3                                                 331     NHC.sub.2 H.sub.4 OH                                                   332     NHCH.sub.3           m.p. 113-114°                              333     N(CH.sub.3).sub.2                                                      334     NHC.sub.2 H.sub.5                                                      335     N(C.sub.2 H.sub.5).sub.2                                               336     NHC.sub.3 H.sub.7 n                                                    337     NHC.sub.4 H.sub.9 n                                                    338                                                                                     ##STR63##                                                             339     N(CH.sub.3)OCH.sub.3                                                    ##STR64##                                                                     340     OH                                                                     341     OCH.sub.3            m.p. 89-93°                                342     OC.sub.2 H.sub.5     n.sub.D.sup.20 1.5340                             343     OCH.sub.2 CHCH.sub.2                                                   344     SCH.sub.2 CHCH.sub.2                                                   345     SCH.sub.3                                                              346     SCH.sub.2 COOCH.sub.3                                                  347     NH.sub.2                                                               348     NHCH.sub.3                                                             349     N(CH.sub.3).sub.2                                                      350     NHC.sub.2 H.sub.5                                                      351     NHCH.sub.2 CHCH.sub.2                                                   ##STR65##                                                                     352     OH                                                                     353     OCH.sub.3                                                              354     OC.sub.2 H.sub.5     n.sub.D.sup.30 1.5167                             355     OC.sub.3 H.sub.7 iso                                                   356     OC.sub.2 H.sub.4 OCH.sub.3                                             357     OCH.sub.2 CHCH.sub.2                                                   358     OCH.sub.2CH                                                            359     SCH.sub.3                                                              360     SC.sub. 2 H.sub.5                                                      361     SCH.sub.2 CHCH.sub.2                                                   362     NH.sub.2                                                               363     N(CH.sub.3).sub.2                                                      364     NHC.sub.2 H.sub.5                                                      365     NHC.sub.2 H.sub.4 OCH.sub.3                                            366     N(CH.sub.3)OCH.sub.3                                                   ______________________________________                                         No.  E      D      Z    B           phys. data                                 ______________________________________                                          ##STR66##                                                                     367  Cl     Br     Cl   OCH.sub.3                                              368  Cl     Br     Cl   OC.sub.2 H.sub.5                                       369  I      H      NO.sub.2                                                                            OCH.sub.3   n.sub.D.sup.25 1.6125                      370  I      H      Cl   OCH.sub.3   n.sub.D.sup.25 1.5995                      371  Br     Br     NO.sub.2                                                                            OCH.sub.3   m.p. 118-120°                       372  CN     Cl     Cl   OCH.sub.3   m.p. 109-111°                       373  Br     CN     Cl   OCH.sub.3   m.p. 135-7°                         374  Cl     H      Cl   OCH.sub.3   b.p. 145-150°/0.04                  375  Cl     H      NO.sub.2                                                                            NH.sub.2                                               376  Br     H      NO.sub.2                                                                            OC.sub.2 H.sub.5                                       377  Br     H      Cl   OCH.sub.2 CHCH.sub.2                                   378  CN     Cl     Br   OCH.sub.3   m.p. 107-9°                         379  CF.sub.3                                                                              Cl     Br   OCH.sub.3                                              380  Cl     CH.sub.3                                                                              Cl   OCH.sub.3                                              381  Cl     CH.sub.3                                                                              Br   OC.sub.2 H.sub.5                                       382  Cl     CH.sub.3                                                                              NO.sub.2                                                                            OCH.sub.3                                              383  Cl     CH.sub.3                                                                              NO.sub.2                                                                            NHCH.sub.3                                             384  CF.sub.3                                                                              H      Br   OCH.sub.3                                              385  CF.sub.3                                                                              Br     Cl   OCH.sub.3                                              386  Br     Br     Br   OCH.sub.3   m.p. 64-6°                          387  Br     Br     NO.sub.2                                                                            OCH.sub.3   m.p. 118-120°                       388  Br     Br     Br   SCH.sub.3                                              389  Br     Br     Cl   OCH.sub.3   m.p. 86-8°                          390  Cl     H      Br   OCH.sub.3   m.p. 80-2°                          391  CF.sub.3                                                                              Br     NO.sub.2                                                                            NH.sub.2                                               392  CF.sub.3                                                                              Br     NO.sub.2                                                                            NHCH.sub.3                                              ##STR67##                                                                     393  Cl     Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                                                           n.sub.D.sup.25 1.5820                      394  CN     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                       395  Cl     CH.sub.3                                                                              NO.sub.2                                                                            OC.sub.2 H.sub.5                                       396  Cl     CH.sub.3                                                                              NO.sub.2                                                                            NH.sub.2                                               397  Br     Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                       398  CF.sub.3                                                                              Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                        ##STR68##                                                                     399  Cl     Cl     NO.sub.2                                                                            OCH.sub.3   m.p. 83-5°                          400  Cl     Cl     NO.sub.2                                                                            NH.sub.2    m.p. 203-5°                         401  Cl     Cl     NO.sub.2                                                                            NHC.sub.2 H.sub.5                                                                          m.p. 124-5°                         402  Cl     Cl     NO.sub.2                                                                            N(CH.sub.3)OCH.sub.3                                                                       m.p. 106-7°                         403  Cl     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.4 OCH.sub.3                                                                 m.p. 71-2°                          404  Cl     Cl     Br   OCH.sub.3   m.p. 81-2°                          405  Cl     CH.sub.3                                                                              NO.sub.2                                                                            OCH.sub.3                                              406  CF.sub.3                                                                              Cl     NO.sub.2                                                                            OCH.sub.3                                              407  CF.sub.3                                                                              H      NO.sub.2                                                                            OCH.sub.2 CHCH.sub.2                                   408  CF.sub.3                                                                              H      Cl   OCH.sub.3                                              409  CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                               ##STR69##                                                                     410  Cl     Cl     Cl   OCH.sub.3   n.sub.D.sup.30 1.5586                      411  Cl     Cl     NO.sub.2                                                                            OCH.sub.3   n.sub.D.sup.30 1.5527                      412  Cl     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                       413  Cl     Cl     NO.sub.2                                                                            NHCH.sub.3                                             414  CF.sub.3                                                                              H      NO.sub.2                                                                            OCH.sub.3                                              415  CF.sub.3                                                                              Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                       416  CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                              417  Br     Br     NO.sub.2                                                                            OCH.sub.3                                              ______________________________________                                         No.     B                    phys. data                                        ______________________________________                                          ##STR70##                                                                     418     OCH.sub.3            m.p. 93-94°                                419     OC.sub.2 H.sub.5                                                       420     OC.sub.2 H.sub.4 OCH.sub.3                                             421     NH.sub.2             m.p. 145-146°                              422     NHCH.sub.3           m.p. 132-134°                              423     N(CH.sub.3).sub.2    m.p. 136-137°                              424     NHC.sub.2 H.sub.5    m.p. 124-126°                              425     N(C.sub.2 H.sub.5).sub.2                                                                            m.p. 75-77°                                ______________________________________                                         No.  E      D      Z    R.sub.1                                                                             A          phys. data                             ______________________________________                                          ##STR71##                                                                     426  Cl     Cl     NO.sub.2                                                                            H    CN         m.p. 118-120°                   427  Cl     Cl     Cl   CH.sub.3                                                                            CN         m.p. 119-120°                   428  Cl     Cl     Cl   H    CN         m.p. 101-3°                     429  Cl     Cl     Cl   CH.sub.3                                                                             ##STR72## m.p. 133-5°                     430  Cl     Cl     Cl   CH.sub.3                                                                             ##STR73##                                        431  Cl     Cl     NO.sub.2                                                                            CH.sub.3                                                                             ##STR74##                                        ______________________________________                                    

The compositions of the present invention are obtained in known manner by homogeneously mixing and grinding active substances of the general formula I with suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances. The active substances can be processed to the following formulations:

solid formulations:

dusts, tracking powders, granules (coated granules, impregnated granules and homogeneous granules);

active substance concentrates which are dispersible in water:

wettable powders, pastes, emulsions;

liquid formulations: solutions.

The concentration of active substance in the above described compositions is between 0.1 and 95%, preferably between 1 and 80%. The rates of application are ordinarily from 0.1 to 10 kg, preferably from 0.25 to 5 kg, of active substance per hectare. The compositions of the present invention can also be mixed with other biocidal active substances or compositions.

The active substances of the formula I can be formulated for example as follows (parts are by weight):

Dusts: The following substances are used to prepare (a) 5% and (b) a 2% dust:

(a)

5 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid methyl ester,

95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground.

Granulate: The following substances are used to prepare a 5% granulate:

5 parts of above active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.25 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin and subsequently evaporated in vacuo.

Wettable Powders: The following constituents are used to prepare (a) a 50%, (b) a 25% and (c) a 10% wettable powder:

(a)

50 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenoxy] propionic acid methyl ester

5 parts of sodium dibutylnaphthylsulphonate

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehyde condensate (3:2:1)

20 parts of kaolin

22 parts of Champagne chalk;

(b)

25 parts of the above active substance

5 parts of sodium oleylmethyltauride

2.5 parts of naphthalenesulphonic acid/formaldehyde condensate

0.5 parts of carboxymethyl cellulose

5 parts of neutral potassium aluminium silicate

62 parts of kaolin;

(c)

10 parts of the above active substance

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The indicated active substance is applied to the corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of excellent wettability and suspension power. By diluting these wettable powders with water it is possible to obtain suspensions of the desired concentration of active substance. Such suspensions are used for controlling weeds and grass-like weeds in crops of cultivated plants by the preemergent method and for treating areas of grass.

Paste: The following substances are used to manufacture a 45% paste:

45 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid methyl ester

5 parts of sodium aluminium silicate

14 parts of cetyl polyglycol ether with 8 moles of the ethylene oxide

1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide

2 parts of spindle oil

10 parts of polyethylene glycol

23 parts of water.

The active substance is homogeneously mixed with the adjuvants in appropriate devices and ground, yielding a paste from which, by dilution with water, it is possible to obtain suspensions of the desired concentration of active substance. The suspension are suitable for treating areas of grass.

Emulsifiable Concentrate: The following ingredients are mixed to manufacture a 25% emulsifiable concentrate:

25 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid isopropyl ester

5 parts of a mixture of nonylphenolpolyoxyethoxy-ethylene and calcium dodecylenesulphonate

35 parts of 3,3,5-trimethyl-2-cyclohexan-1-one

35 parts of dimethyl formamide.

This concentrate can be diluted with water to give emulsions in the desired concentrations.

Instead of using the respective active substance indicated in the foregoing formulation examples, it is also possible to use another of the compounds comprised by the formula I.

The active substances of the invention are also of interest for combination with an number of hercides of the phenylurea and triazine series for use in cereal crops, maize, sugar cane, and in fruit culture and viticulture.

The active substances of the formula I are distinguished by a very pronounced preemergent herbicidal action and are thus also strong germination inhibitors.

The following test methods were employed to established the usefulness of the compounds of the formula I as herbicides (pre- and postemergent).

PREEMERGENT HERBICIDAL ACTION (Germination Inhibition)

In a greenhouse, immediately after sowing the test plants in seed dishes the surface of the soil is treated with an aqueous suspension of the active substances obtained from a 25% wettable powder. A concentration was used, which corresponded to 4 kg of active substance per hectare. The seed dishes are then kept in the greenhouse at 22°-25° C. and 50 to 70% relative humidity. The test was evaluated 3 weeks later according to the following rating:

1=plants have not germinated or are totally withered

2-8=intermediate stages of damage

9=plants undamaged (as untreated control).

The results are resumed in the table below:

    ______________________________________                                         Compound          Sinapis    Setaria                                                                              Stellaria                                   number     oats   alba       italica                                                                              media                                       ______________________________________                                         2          8      3          2     2                                           14         9      2          2     3                                           35         9      4          1     2                                           53         7      3          2     2                                           87         2      1          1     3                                           112        2      1          1     1                                           114        1      2          1     2                                           115        1      1          1     1                                           127        2      2          1     2                                           144        9      1          1     5                                           149        7      2          2     2                                           192        9      2          1     1                                           201        9      4          1     1                                           210        2      1          1     1                                           261        2      2          1     7                                           297        1      1          1     1                                           399        3      1          3     9                                           418        9      1          1     1                                           ______________________________________                                    

POST-EMERGENT HERBICIDAL ACTION (Contact Herbicide)

A number of weeds and cultivated plants, both mono- and dicotyledonous, were sprayed after emergence in the 4- to 6-leaf stage with an aqueous active substance emulsion in a rate of 4 kg of active substance per hectare and kept at 24°-26° C. and 45-60% relative humidity. The test was evaluated, as in the preemergent test, 15 days after treatment in accordance with the same rating.

The results are resumed in the table below:

    ______________________________________                                         Compound        Setaria  Lolium Sinapis                                                                               Stellaria                               No.     oats    italica  perenne                                                                               alba   media                                   ______________________________________                                         1       2       1        1      1      1                                       2       4       1        2      1      1                                       3       4       1        3      2      2                                       12      7       1        3      1      2                                       16      6       2        3      1      2                                       19      5       1        3      1      2                                       22      6       2        6      2      1                                       27      4       1        2      1      1                                       28      6       1        5      3      2                                       35      5       1        3      1      1                                       41      4       5        4      2      2                                       43      4       1        4      1      1                                       53      5       2        6      1      2                                       55      6       1        3      1      1                                       66      4       1        4      2      3                                       92      2       1        1      1      3                                       95      4       2        3      1      6                                       98      4       1        1      1      2                                       111     4       2        2      1      2                                       113     2       2        2      2      3                                       115     2       2        5      1      5                                       128     2       1        3      1      1                                       129     7       1        6      1      6                                       141     4       3        4      1      4                                       149     2       1        2      1      1                                       192     3       1        1      1      1                                       194     3       1        1      1      1                                       196     3       1        1      1      1                                       200     4       1        2      1      1                                       201     7       1        3      1      1                                       202     6       2        4      2      2                                       204     5       2        3      2      2                                       210     1       1        1      1      1                                       261     1       1        1      1      1                                       297     1       1        1      1      1                                       372     4       2        4      2      1                                       387     2       1        1      1      1                                       399     1       1        2      1      3                                       403     2       1        2      1      8                                       418     4       1        2      1      4                                       426     2       1        3      1      4                                       ______________________________________                                     

We claim:
 1. A compound of the formula: ##STR75## wherein E is halo or trifluoromethyl;D is hydrogen, halo or nitro; Z is halo or nitro; R₁ is hydrogen, alkyl of 1 to 4 carbon atoms, or methoxymethyl; R₄ is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 3 to 8 carbon atoms, alkynyl of 3 to 8 carbon atoms, or alkyl of 1 to 4 carbon atoms substituted with alkoxy of 1 to 4 carbon atoms; and R₅ is hydrogen, alkoxy of 1 to 4 carbon atoms alkyl of 1 to 4 carbon atoms, alkenyl of 3 to 8 carbon atoms, alkynyl of 3 to 8 carbon atoms, or alkyl of 1 to 4 carbon atoms substituted with alkoxy of 1 to 4 carbon atoms.
 2. A compound according to claim 1 wherein R₁ is methoxymethyl.
 3. A compound according to claim 2wherein E is chloro or trifluoromethyl; D is chloro or nitro; Z is chloro, bromo or nitro; R₄ is hydrogen, methyl or ethyl; and R₅ is hydrogen, methoxy, methyl, ethyl or methoxyethyl.
 4. A compound according to claim 1 wherein R₅ is methoxy or methoxyethyl.
 5. A compound according to claim 4wherein E is chloro or trifluoromethyl; D is chloro or nitro; Z is chloro, bromo or nitro; R₁ is hydrogen, methyl, ethyl, or methoxymethyl, and R₄ is hydrogen, methyl or ethyl.
 6. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl-2-oxy)-6-chlorophenoxy]-butanoic acid N-methyl-N-methoxyamide.
 7. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl-2-oxy)-6-bromophenoxy]-propionic acid amide.
 8. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl-2-oxy)-6-bromophenoxy]-propionic acid N-ethylamide.
 9. A compound according to claim 1wherein E is chloro or trifluoromethyl; D is chloro or nitro; Z is chloro, bromo or nitro; R₁ is methyl, ethyl or methoxymethyl; R₄ is hydrogen, methyl or ethyl; and R₅ is hydrogen, methyl or ethyl.
 10. The compound according to claim 1 which is α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]-propionic acid amide.
 11. The compound according to claim 1 which is α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]-propionic acid methylamide.
 12. The compound according to claim 1 which is α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]-propionic acid N-methyl-N-methoxyamide.
 13. The compound according to claim 1 which is α-[3-(3'-chloro-5'-trifluoromethylpyridyl-2'-oxy)-6-nitrophenoxy]-propionic acid.
 14. A compound according to claim 6 in which D, E and Z are chlorine, and R₁ is methyl.
 15. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl-2-oxy)-6-chlorophenoxy]-propionic acid N-methyl-N-methoxyamide.
 16. A compound according to claim 6 in which D and E are chlorine, Z is nitro, and R₁ is methyl.
 17. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl)-2-oxy)-6-nitrophenoxy]-propionic acid dimethylamide.
 18. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl)-2-oxy)-6-nitrophenoxy]-propionic acid ethylamide.
 19. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl)-2-oxy)-6-nitrophenoxy]-propionic acid methoxyethylamide.
 20. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl-2-oxy)-6-nitrophenoxy]-propionic acid N-methyl-N-methoxyamide.
 21. The compound according to claim 1 which is α-[3-(3,5-dichloropyridyl)-2-oxy)-6-nitrophenoxy]-propionic acid pent-4-ynylamide.
 22. A compound according to claim 6 in which D and E are chlorine, Z is bromine, and R₁ is methyl.
 23. A compound according to claim 6 in which D and Z are chlorine, E is trifluoromethyl, and R₁ is methyl.
 24. A compound according to claim 6 in which D is chlorine, E is trifluoromethyl, Z is nitro, and R₁ is methyl.
 25. The compound according to claim 1 which is α-[3-(3-chloro-5-trifluoromethylpyridyl)-2-oxy)-6-nitrophenoxy]-butyric acid amide.
 26. The compound according to claim 1 which is α-[3-(3-chloro-5-trifluoromethylpyridyl-2-oxy)-6-nitrophenoxy]-butyric acid methylamide.
 27. A herbicidal composition which contains as active ingredient a herbicidally effective amount of a compound according to claim 1 together with an inert carrier.
 28. A method for controlling weeds at a locus, which comprises applying to said locus a herbicidally effective amount of a compound according to claim
 1. 